[Show abstract][Hide abstract] ABSTRACT: To investigate the effects of the microstructure and powder compositions for the micro-porous layer (MPL) of an anode on the cell performance of a direct methanol fuel cell (DMFC) using a highly concentrated methanol solution up to 7 M, various powders and their compositions were applied as a filler of the MPL in the membrane electrode assembly (MEA). Several nano- and microstructured carbons such as commercial carbon black (CB), spherical activated carbon (AC), multi-walled carbon nanotube (MWCNT), and platelet carbon nanofiber (PCNF) were selected with different morphology and surface properties, and a meso-porous silica (one of SBA series) was also included for its porous and hydrophilic properties. The coating morphology and physical properties such as porosity and gas permeability were measured, and electrochemical properties of MEA with the MPL were examined by using current–voltage polarization, electrochemical impedance spectroscopy, and voltammetric analyses. A mixture of different carbons was found to be effective for lowering methanol crossover with sustaining electrical conductivity and gas permeability. A MEA with modified-anode MPLs made of CB (50 vol%) and PCNF (50 vol%) powders showed a maximum power density of 67.7 mW cm−2 under operation with a 7 M concentration of methanol.
International Journal of Hydrogen Energy 06/2013; 38(17):7159–7168. · 3.55 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Freeze-thaw cycles were used to investigate performance degradation in direct methanol fuel cells (DMFC). The freeze-thaw cycles were carried out across the temperature range of −32 °C–60 °C. The details of the performance degradation were analyzed by comparing the change of polarization of each electrode and the electrochemical impedance spectrum according to the number of freeze-thaw cycles. It was found that freeze-thaw cycles caused the increase in the cathode overpotential to affect performance degradation and the increase in the charge transfer resistance which means distinct damages in the triple phase boundary of the catalyst layer. Different purging scenarios before freezing were adopted, namely the cathode purge and the anode–cathode purge, to reduce any performance degradation caused by the freeze-thaw cycles. The cells purged by nitrogen gas were found to have less performance loss than the cells that were not purged during the freeze-thaw cycles. The changes in the cell resistance and the cathode electrochemical surface areas were also smaller when the cells were purged compared with those cells that were not purged. The introduction of air purging had similar positive influences with nitrogen purging on the performance of the DMFCs and their impedance. It was also determined that air was better at purging only the cathode than purging both electrodes.
International Journal of Hydrogen Energy 11/2012; 37(22):17268–17274. · 3.55 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The chemical stability and durability of PtRu catalysts supported on carbon nanofibers (CNFs) for the anode electrode of a direct methanol fuel cell (DMFC) are investigated by Pt and Ru dissolution tests in sulfuric acid and long-term performance tests of a single cell discharging at a constant current density of 150 mA cm−2 for approximately 2000 h. A CNF with a herringbone-type structure, which is characterized by the alignment of graphene symmetrically angled to the fiber axis, was selected as the catalyst support because it has an edge-rich surface and a high surface area. In the metal dissolution test, the PtRu/CNF catalysts showed 1.5–2 times lower Ru leaching than a tested commercial catalyst (supported on activated carbon). The results of long-term performance tests also prove the higher durability of the anode catalyst compared with the commercial catalyst, when the anode polarization is compared before and after operation for 2000 h. Some analytical measurements, including X-ray diffraction, energy dispersive spectroscopy, and transmission electron microscopy were conducted to study the degradation of the catalyst activity.
[Show abstract][Hide abstract] ABSTRACT: Various silica particles were adopted as catalyst supports, and silica-supported PtRu catalysts were evaluated as catalysts for the anode of direct methanol fuel cells at methanol concentrations of 1–10 M through single cell tests. Compared to a carbon black supported Pt–Ru catalysts, the silica-supported Pt–Ru catalysts exhibited higher performance in MEA, especially with high concentration over 3 M, and the maximum power density reached to 90 mW cm−2 and 60 mW cm−2 with 5 M and 10 M, respectively, which were 1.5 and 3 times higher than the reference carbon black supported catalysts. It was found that the silica particles as a catalyst support have a significant effect on reduction of methanol crossover and control of fuel feeding. Such a high performance in the operation with high concentrations was confirmed in the long-term durability test.
[Show abstract][Hide abstract] ABSTRACT: According to the conventional MEA test, methanol and water crossover are the main factors to determine performance of a passive DMFC. Thus, to ensure the high cell performance of a passive DMFC using high concentration methanol of 50–95 vol%, the MEA in this study introduces the barrier layer to limit the crossover of high concentration methanol, a hydrophobic layer to reduce water crossover, and a hydrophilic layer to enhance the water recovery from the cathode to the anode. The functional layers of the MEA have the effect of improving the performance of the passive DMFC by decreasing the methanol and water crossover. In spite of the operation with 95 vol% methanol, the MEA with multi-layer electrodes for high concentration methanol DMFCs shows a maximum power density of 35.1 mW cm−2 and maintains a high power density of 30 mW cm−2 (0.405 V) under constant current operation.
[Show abstract][Hide abstract] ABSTRACT: The outer micro-porous layer (MPL) between the gas diffusion layer and channel of the bipolar plate was studied for both sides of the electrodes in DMFC, with particular attention to the effects of the hydrophobicity of the MPL on mass transport as well as cell performance. Water-transport behavior from the electrodes to the channel was observed through the transparent window of the single cell with membrane-electrode assemblies (MEAs) including three combinations of outer MPLs. The crossover amount of methanol as well as water through the membrane was measured, and the mass balance, based on the measured flux, was established to understand the mass transport in MEAs. The design of outer MPLs is discussed for the best cell performance.
[Show abstract][Hide abstract] ABSTRACT: Highly dispersed Pd nanoparticles were prepared by borohydride reduction of Pd(acac)(2) in 1,2-propanediol at an elevated temperature. They were uniformly dispersed on carbon black without significant aggregation. X-ray diffraction showed that carbons from the Pd precursor dissolved in Pd, increasing its lattice parameter. A modified reduction process was tested to remove the carbon impurities. Carbon removal greatly enhanced catalytic activity toward the oxygen reduction reaction. It also generated an inconsistency between the electronic modifications obtained from X-ray photoelectron spectroscopy and the electrochemical method. CO displacement measurements showed that the formation of Pd-C bonds decreased the work function of the surface Pd atoms.
[Show abstract][Hide abstract] ABSTRACT: Carbon-supported Pt nanoparticles with various loading of Pt are prepared by a novel seed-mediated growth method using hydroquinone (HQ) assisted selective deposition. The structural and morphological dependence of the Pt nanoparticles on the catalytic activity in oxygen reduction reaction (ORR) is investigated. The analysis of core-level X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) cannot elucidate the origin of the large enhancement of the ORR activity. In contrast, electrochemical measurements of the CO-displacement charge and the concomitant CO adlayer oxidation behavior prove that the selective deposition of additional Pt contributed to the decrease of surface defects and to the increase of the onset potential for OH adsorption.
Journal of electroanalytical chemistry 11/2011; 662(1):70-79. · 2.67 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: CrN/Cr-coated stainless steel (STS) 316L is investigated as the material for a metal bipolar plate for a direct methanol fuel cell (DMFC) under actual operating circumstances. Protective coating layers of CrN/Cr are formed on STS 316L using an unbalanced magnetron (UBM) DC sputter via Cr target in an effort to improve the corrosion resistance and long-term stability of the STS 316L. In a corrosion resistance test, the CrN/Cr-coated STS 316L shows much better corrosion resistance than bare STS 316L in simulated electrolytic environments under anodic and cathodic potentials relevant to DMFCs. The interfacial contact resistance (ICR) between CrN/Cr-coated 316L and carbon paper decrease to 4mΩcm2 at a compaction force of 150Ncm−2 compared to bare STS 316L (570mΩcm2). The CrN/Cr-coated STS 316L cell has better cell performance compared to the bare STS 316L cell. Furthermore, the CrN/Cr-coated STS 316L cell exhibit low voltage losses of 38.2μVh−1 under long-term operation of 760h. These results show that the CrN/Cr-coated STS 316L, demonstrating its feasibility for use as a metal bipolar plate in a DMFC under actual operating circumstances.
[Show abstract][Hide abstract] ABSTRACT: Reported herein is a simple template method for preparing mesoporous carbons (MPCs) from a mesophase pitch, using homemade nano-sized MgOs and MgO-carbon nanotube (CNT) composites as templates. Nano-sized MgO particles containing iron-molybdenum were synthesized through the heat treatment of the precursor ash, and the MgO-CNT composites were prepared via catalytic chemical vapor deposition of CH4 over the MgO-based particles. MPCs with a high surface area of 443-578 m2/g were obtained through the heat treatment of well-mixed mesophase pitch-MgO (or MgO-CNT), followed by mild-acid treatment to remove the MgO and other catalyst components. All the materials (the precursors, nano-particles, and MPCs) were analyzed via powder X-ray diffraction, N2 adsorption-desorption isotherms, scanning electron microscopy, and high resolution transmission electron microscopy. The formation of the pore structure in the MPCs is discussed, and the potential application of the MPC-CNT composite is demonstrated through cyclic voltammetry.
Journal of Nanoscience and Nanotechnology 07/2011; 11(7):5761-8. · 1.15 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: A series of sulfonated poly(fluorenyl ether nitrile oxynaphthalate) (SPFENO) copolymers with different degree of sulfonation (DS) are synthesized via nucleophilic polycondensation reactions with commercially available monomers. Incorporation of the naphthalanesulfonate group into the copolymers and their copolymer structures are confirmed by 1H NMR spectroscopy. Thermal stability, mechanical properties, water uptake, swelling behavior, proton conductivity and methanol permeability of the SPFENO membranes are investigated with respect to their structures. The electrochemical performance of a direct methanol fuel cell (DMFC) assembled with the SPFENO membrane was evaluated and compared to a DMFC with a Nafion 117 membrane. The DMFC assembled with the SPFENO membrane of proper DS exhibits better electrochemical performance compared to the Nafion 117-based cell.
Fuel and Energy Abstracts 07/2011; 36(14):8492-8498.
[Show abstract][Hide abstract] ABSTRACT: Water flooding phenomena in the cathode of direct methanol fuel cells were analyzed by using electrochemical impedance spectroscopy. Two kinds of commercial gas diffusion layers with different PTFE contents of 5 wt% (GDL A5) and 20 wt% (GDL B20) were used to investigate the water flooding under various operating conditions. Water flooding was divided into two types: catalyst flooding and backing flooding. The cathode impedance spectra of each gas diffusion layer was obtained and compared under the same conditions. The diameter of the capacitive semicircle became larger with increasing current density for both, and this increase was greater for GDL B20 than GDL A5. Catalyst flooding is dominant and backing flooding is negligible when the air flow rate is high and current density is low. An equivalent model was suggested and fitted to the experimental data. Parameters for catalyst flooding and backing flooding were individually obtained. The capacitance of the catalyst layer decreases as the air flow rate decreases when the catalyst flooding is dominant.
Journal of Nanoscience and Nanotechnology 07/2011; 11(7):5788-94. · 1.15 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The electrocatalytic activity of nitrogen-doped carbon nanofibers (N-CNFs), which are synthesized directly from vaporized acetonitrile over nickel-iron based catalysts, for oxygen reduction reaction (ORR), was investigated. The nitrogen content and specific surface area of N-CNFs can be controlled through the synthesis temperature (300-680 degrees C). The graphitization degree of N-CNFs also are significantly affected by the temperature, whereas the chemical compositions of nitrogen species are similar irrespective of the synthesis conditions. From measurement of the electrochemical double layer capacitance, the surface of N-CNFs is found to have stronger interaction with ions than undoped-carbon surfaces. Although N-CNFs show higher over-potential than Pt catalysts do, N-CNFs were observed to have a noticeable ORR activity, as opposed to the carbon samples without nitrogen doping. The activity dependency of N-CNFs on the content of the nitrogen with which they were doped is discussed, based on the experiment results. The single cell of the direct methanol fuel cell (DMFC) was tested to investigate the performance of a membrane-electrode assembly that includes N-CNFs as the cathode catalyst layer.
Journal of Nanoscience and Nanotechnology 07/2011; 11(7):6350-8. · 1.15 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Carbon nanofibers (CNFs) with uniquely oriented channels were prepared via selective catalytic gasification in air at 450 and 500 degrees C, using Pt or Ru nano particles as catalysts. Catalytic gasification was chosen because it can selectively generate channels in the vicinity of the catalyst particles at relatively low temperatures, where thermal oxidation does not intensively occur. The structures and surface properties of the CNFs were examined via X-ray diffraction, analysis of the nitrogen adsorption-desorption isotherms, and high-resolution transmission electron microscopy. The effects of the catalyst species and loading amount on the formation of pores (channels) were investigated. The gasification mechanism, especially the channeling direction, throught the selection of the gasification catalysts, is discussed based on the results. This process can be effectively utilized for preparation of porous carbons, which have a well-aligned graphitic structure, and also channel-type pores can be designed by selection of gasification catalysts and conditions. The present porous CNF can be applied for catalyst support in fuel cells, without further treatment (e.g., acid treatment for the removal of metallic components).
Journal of Nanoscience and Nanotechnology 07/2011; 11(7):5775-80. · 1.15 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The operation characteristics of a direct methanol fuel cell (DMFC) are investigated at low temperatures of −5 °C and −10 °C by using a laboratory-made 10-cell stack. The stack is operated only by heat generation of internal exothermic reactions without any heating device and additional insulation means, to examine behaviors of the stack performance at low temperatures. The self-heating stack is successfully operated in a stable manner at −10 °C by control of the operation modes. An appropriate operation strategy using the fuel switching as well as selection of the operation modes is proposed, and possibility and limitation for operation of DMFC stacks by self-heating under cold conditions are discussed, based on the results.
International Journal of Hydrogen Energy 05/2011; 36(9):5655–5665. · 3.55 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: In this work, we studied the characteristic variations of catalyst supports caused by mechanical milling and their electrochemical application in fuel cells. Two different catalyst supports, carbon black (XC-72R) and K20 (mesoporous carbon), were crushed and dispersed by mechanical milling using a bead mill. The bead mill operated with 0.3μm zirconia beads at the rate of 3500rpm for 30min. The secondary particle size of the crushed catalyst supports ranged from around 0.1μm to 10μm. The secondary particle size of the catalyst supports after crushing represents a decrease of approximately 10% compared with that of raw catalyst supports. To confirm the role of the catalyst supports in the direct methanol fuel cell (DMFC), Pt and Ru were loaded onto these catalyst supports using an impregnation method. In the single cell test, Pt–Ru/XC-Bead and PtRu/K20-Bead showed power densities of 135mW/cm2 and 144mW/cm2 under air at 60°C, respectively. The performance values of these catalysts, which were fabricated using reformed catalyst supports, were 10% to 20% higher than those of raw catalyst supports. As a result, the catalyst supports crushed by the bead mill helped to improve the electrochemical performance of the direct methanol fuel cell.
[Show abstract][Hide abstract] ABSTRACT: The influences of the gas diffusion layer (GDL) properties on the current distributions of a direct methanol fuel cell are investigated. Cathode GDLs with different hydrophobicity/hydrophilicity, air permeability, microporous layer (MPL), thickness, and texture properties are examined. Among the GDLs examined, a thin hydrophobic GDL with an MPL has the most homogeneous current distribution, which is primarily ascribed to the better water management capabilities of the cathode GDL properties. The differences in the current distribution among the different GDLs are more apparent when the air flow rate and loaded current are lower. The effect of the membrane thickness on the current distributions is also investigated. Among the membranes examined, Nafion® 112 has different current distributions from the others, whereas there is no noticeable difference between the current distributions with Nafion® 115 and Nafion® 117. The current distribution with Nafion® 112 is most affected by the enhanced methanol crossover and the high mixed potential.
[Show abstract][Hide abstract] ABSTRACT: This study addresses how durability of direct methanol fuel cells (DMFCs) is involved with the electrode structures of membrane electrode assembly (MEA) with different porosity and microstructures. The different electrode structures of the MEAs (porous (MEA-1) and dense (MEA-2) electrode structure) bring about the difference in the reaction kinetics associated with the electrochemical active surface area (ECSA) and in mass transport on the electrodes. The dense electrode structures of the MEA-2 cause the continual non-uniformity of the mass transport-related phenomena at the cathode, and thereby the catalysts of the MEA-2 experience much severer particle growth and agglomeration to decrease ECSA and activity of the catalysts. During the long-term operation, the decay rate of the MEA-2 was faster by more than three times compared to the MEA-1 with the relatively porous electrode structures. These results show that an electrode structure of a MEA is an important factor to govern durability of DMFCs.
Fuel and Energy Abstracts 01/2011; 36(23):15313-15322.